Method of preparing fluorine perchlorate

ABSTRACT

Process of preparing fluorine perchlorate by reacting elemental fluorine with an alkali metal perchlorate in a liquid moderator and recovering fluorine perchlorate as a product of the process.

United States Patent Grakauskas 51 Feb. 1, 197 2 [54] METHOD OF PREPARING FLUORINE PERCHLORATE [56] References Cited [72] I Inventor: Vyhutu Grahuskls, Arcadia, Calif. OTHER PUBLICATIONS [73] Assignee: Aemjet-Genenl Corporation, El Monte, Rohrback et al., The Preparation of Fluorine Perchlorate lm from Fluorine and Perchloric Acid," Journal of the American 7 Chemical Society, Vol. 49, No. 3, March 1947, pp. 677- 681. [22] Filed: Aug. 3, 1970 Primary Examiner-Earl C. Thomas [21] Appl' Attorney-Edward O. Ansell, Mark C. Jacobs and D. Gordon Related U.S.Appllcation um Angus [60] Division of Ser. No. 744,62l, July ll, 1968, Pat. No. [57] ABSTRACT 3,556,726, which is a continuation-in-part of Ser. No. 204 663 June 19 1962 abandoned rocess of preparing fluorine perchlorate by react ng elemental fluorine with an alkali metal perchlorate in a liquid U 8 Cl 23/203 R 252/367 moderator and recovering fluorine perchlorate as a product of th 511 lm. Cl. ..C01b 11/14, cow 11/24 8 process [58] Field of Search ..23/203, 85, 367 5 Claims, No Drawings METHOD OF PREPARING FLUORTNE PERCHLORATE This application is a divisional of application Ser. No. 744,621, filed July 11, 1968, now US. Pat. No. 3,556,726 which is a continuation of application Ser. No. 204,663, filed June 19, l962, now abandoned.

This invention relates to a novel method of preparing nonionic inorganic'fluoro compounds. This invention further relates to certain novel inorganic compounds.

lt is an object of this invention to prepare nonionic inorganic fluoro compounds in a novel manner. It is another object of this invention to employ novel reaction conditions whereby fluorine groups can be introduced selectively into inorganic compounds. Still another object of this invention is to prepare novel nonionic inorganic fluoro compounds. These and other objects of thisinvention will be apparent from the detailed description which follows.

The nonionic inorganic fluoro compounds are prepared according to the process of this invention by reacting certain ionic inorganic salts with fluorine, the reaction proceeding in accordance with the following general equation:

wherein M is a metal cation having a valence of from +1 to +5, and A is an inorganic moiety selected from the group consisting of azide, nitrate, nitrite, isocyanate, chlorate, perchlorate, cyanide, N N 0,, N 0 and N 0 and u, v, w, y and z are small whole numbers of from 1 to about 5. Normally in the above equation, 14 times the valence of M equals v times the valence of A, w times the valence of F equals x times the valence of A and y times the valence of M equals 2 times the valence of F. However, this is not always the case. Thus, an exception to this general rule may be seen in the case where M F is mercurous fluoride (Hg F In the above equation, F A, are the nonionic fluoro compounds, as is evidenced by their general insolubility in water, and M F is an ionic byproduct.

While not bound by any theory, it appears that in the process of this invention, the diatomic fluorine divides into an anion portion and a cation portion. The cation portion reacts with the anion A to form the compound F,,.A,., while the anion portion reacts with cation M to form M,,F

Illustrative of the metal cations suitable for use in the above reaction are the metals of groups IA and A of period 2, groups M, "A and "IA of period 3, groups lA, llA, lllA, lVA, l8, "B, "[8, NB, VB, VlB, and VllB of period 4, groups lA, MA, MA, IVA, VA, IB, [[3, Hi8, lVB, VB, W3 and VllB of period 5, groups lA, llA, lllA, lVA, VA, WA, IB, llB, lllB, lVB, VB, VIB and VllB of period 6, and all of the elements of group Vlll of the periodic table as it appears in the Handbook of Chemistry and Physics, 42nd Edition, pp. 448 and 449. Specific examples of such metals are sodium, potassium, beryllium, manganese, calcium, barium, titanium, zirconium, tin, lead, vanadium, antimony, bismuth, chromium, molybdcnum, tungsten, manganese, iron, cobalt, nickel, platinum, copper, silver, gold, mercury, cadmium, zinc, aluminum, etc.

Preferred metals are those in periods 2-4, i.e., those elements having atomic numbers 3, 4, 11-13 and 19-32. More preferably, M is an alkali metal cation such as lithium, sodium or potassium.

Illustrative of the compounds which may be fluorinated in accordance with the above reaction are sodium azide, sodium cyanide, potassium nitrate, ferric nitrite, potassium isocyanate, aluminum chlorate, calcium perchlorate, stannous nitrate and barium nitrite.

It should be understood that in the foregoing reaction essentially any inorganic salt which will react with fluorine to form a stable nonionic inorganic fluoro compound may be used. Thus the compounds specifically enumerated above should be regarded as merely illustrative ofthe invention.

Typical nonionic inorganic fluoro compounds which can be prepared according to the process of our invention are azine fluoride, fluorine nitrate, nitryl fluoride, fluoro isocyanate, perchloryl fluoride, fluorine perchlorate, cyanogen fluoride, etc.

Among the compounds having the formula F,,.A,, and prepared according to the above-described process of this in vention, are novel nonionic inorganic fluoro compounds having the generic formula F N O., wherein q is an integer of from 3 to 6 inclusive. These novel compounds have the formulae F N O;,, F N O.,, IQN O and F N O These compounds are prepared according to the process of this invention by reacting fluorine with compounds of the l'or mula M N O wherein M and q are as previously defined.

The aforementioned reactions of this invention are carried out in a substantially inert moderator. The term substantially inert" is used throughout the specification and claims and is intended to include any moderator which is less reactive with fluorine than the inorganic salts M,,A,- being fluorinated.

The most suitable substantially inert moderators are those which are less than one-quarter as reactive with fluorine as are the salts M,,A,.. The moderator of this invention is any polar or nonpolar material in which the inorganic salt M,,A,. being fluorinated is at least partially soluble. Thus the moderator may be a complete solvent for the material being fluorinated. Likewise, the moderator may be a material in which the inorganic salt forms only a partial suspension. Preferably, although not necessarily, the salt M A,. is soluble in the moderator at least to the extent of 1 part by weight per parts by weight of moderator. Use of the moderator is an essential part of the fluorination reaction of this invention. The moderator serves not only as a carrier for the reaction but is also essential to the controlled fluorination of the inorganic salt.

I am not certain as to the exact mechanism by which the moderators control the fluorination. However, the moderator is known to serve as more than a carrier for the reaction since omission ofthe moderator results in rapid random fluorination of the salt, leading to extensive decomposition and contamination of the ultimate product. Further, the moderator promotes selective fluorination, i.e., the fluorination will occur only at the most reactive site in the inorganic salt.

The specific moderator chosen is not critical, and its selection depends upon such factors as cost, availability, inertness and solvent characteristics.

The preferred moderators are those polar and nonpolar materials which are liquids within the temperature range of" about 40 to about +40 C. This does not mean that my moderators must be liquid throughout this entire range. Rather, my preferred moderators are liquid over at least some portion of this range; that is, they have a normal melting point either below or within this range.

Typical of the types ofmoderators suitable in the practice of this invention are the hydrocarbon alkanes and especially the hydrocarbon alkanes having from five to about 10 carbon atoms, such as pentane, hexane, octane, nonane and dccane. Another group of suitable moderators are the haloalkanes having from one to about eight carbon atoms such as methylene dichloride, ethylene chloride, chloroform and carbon tetrachloride. Still another class of moderators are the aromatic hydrocarbons having from six to about 12 carbon atoms such as benzene, toluene, the otho, meta and para isomers of xylene. The chlorinated aromatic hydrocarbons containing six to 12 carbon atoms may also be used. lllustrative of these are monochlorobenzene and chlorotoluene.

Other suitable moderators include the aliphatic ketones, having the formula ll a-o-a the ethers having the formula ROR and the dialkyl substituted amides having the formula o it ll It N wherein in the above formula the R groups are alkyl, and preferably lower alkyl having from one to about eight carbon atoms such as methyl, ethyl, pentyl and octyl. Specific ketones include dimethyl keytone, diethyl keytone and methyl, ethyl keytone. The ethers include dimethyl ether, diethyl ether and diisopropyl ether. The substituted amides include dimethyl formamide, diethyl formamide and dimethyl acetamide.

Still other moderators are water, the lower alkanols having from one to about six carbon atoms and the lower alkylene glycols having from one to about six carbon atoms. Suitable lower alkanols and alkylene glycols include methanol, ethanol, isopropanol, ethylene glycol, propylene glycol and butylene glycol.

Preferred among the foregoing moderators are the polar solvents such as water, the lower alkanols and lower alkylene glycols.

It is to be understood that mixtures of any of the foregoing moderators may be employed in the practice of this invention. Water is the preferred moderator because of its low cost and ready availability. However, lower aliphatic alcohols such as methanol, ethanol, and isopropanol have been found to give very good results. It is surprising that the fluorination reaction can be carried out in lower aliphatic alcohols since the introduction of fluorine into the low aliphatic alcohol would normally be expected to cause fires and explosions. Fluorination reactions in this invention were found to proceed very satisfactorily in the lower aliphatic alcohols.

The amount of the moderator employed is not critical. Normally the weight ratio of moderator to the ionic salt being fluorinated is within the ratio from about 0.5 to 200, and more preferably within the range from about 1.0 to about 20.

The temperature at which these fluorination reactions can be carried out is not critical. Normally it is desirable to keep the temperature as low as possible in working with fluorine. Thus the preferred reaction temperature is between about -l to about +40 C. More preferably, the fluorination reaction is carried out between the temperatures of about 5 and +5 C The fluorine gas used in this invention can sometimes be diluted with an inert gas such as helium or nitrogen so as to improve the control ofthe rate offluorine addition.

In the fluorination reactions of this invention proportions of the reactants may be varied over a wide range. Normally the inorganic salt and fluorine should be used in approximately stoichiometrically equivalent amounts since the use of excessive fluorine can cause extensive reaction with the moderator resulting in undesirable contamination ofthe desired nonionic inorganic fluoro compound.

Many of the inorganic nonionic fluoro compounds of this invention (F,,.A are gases, and are isolated by collection in a cold trap or series of such traps in a conventional manner.

The fluorinations of this invention may be carried out in any conventional reactor. However, for long reactor life, those portions which can come in contact with fluorine should be coated with a material such as nickel or polyethylene.

The inorganic fluoro compounds produced according to this invention which are nongaseous may be isolated from the reaction medium in conventional manner, i.e., by filtration, crystallization, extraction and/or distillation.

Fluorination reactions of this invention may be carried out under any suitable pressure. Normally atmospheric pressure is used since it is most convenient. However it may be sometimes desirable to conduct the fluorination under elevated pressure in order to increase the solubility of the fluorine in the moderator. In other cases it may be desirable to operate the process at reduced pressure so as to facilitate the removal of the gaseous product. Thus the operator may vary the pressure to suit the particular moderator and ionic material, M,,A,., being fluorinated.

The examples which follow are presented only for purposes of illustration and should not be regarded as limitative of the scope of my invention in any way. In the examples percentages are by weight unless otherwise indicated.

EXAMPLEl Preparation ofAzine Fluoride showed it to be axine fluoride.

EXAMPLE ll Preparation ofCyanogen Fluoride Sodium Cyanide was fluorinated following the reaction conditions described in example I, using water as the moderator. The infrared spectrum analysis of the gas produced in this reaction showed the product to be cyanogen fluoride.

When the foregoing example is repeated, using potassium isocyanate in lieu of sodium cyanide, fluoro isocyanate is obtained in good yield.

EXAMPLE Ill Preparation of F- N O;

Following the conditions of example I, K N O is fiuorinated, using hexane as the moderator. The infrared spectrum analysis ofthe product shows it to be F. .N O

When the above example is repeated, using Li N .O,, Fe (N O);r and Al- (N O,,-) in lieu of K N O;,; F N. .O,,, F N Q- and F N O respectively, are obtained in good yield.

When K N O is fluorinated, using first benzene and then dimethyl acetamide as the moderator, in place of hexane, satisfactory results are obtained.

EXAMPLE lV Preparation of Nitryl Fluoride A stream of fluorine l-2 liters per hour) diluted with helium (10 liters per hour) is passed at about 0-15" C. into a solution of 5 grams of potassium nitrite in about ml. of ethanol. The reaction is continued for a period of about 10 minutes. The product is collected in a cooled evacuated container. Analysis of this product shows it to be nitryl fluoride.

When the foregoing example is repeated, using methanol and ethylene glycol, respectively, as the moderator, similar results are obtained.

When the proceeding example is repeated, using magnesium nitrate in lieu of potassium nitrite, and dimethyl acetamide, as the moderator, fluorine nitrate is obtained in good yield.

EXAMPLE V Preparation of Perchloryl Fluoride Potassium chlorate was fluorinated following the reaction conditions described in example I. Water was used as the moderator. The infrared spectrum analysis of the gas produced in this reaction showed it to be identical with the infrared spectrum ofa sample ofcommercial FC 1 0 When example V is repeated, using dimethyl ketone in lieu of water as the moderator, perchloryl fluoride is again obtained in good yield.

EXAMPLE Vl Preparation of Fluorine Perchlorate One part of nickel perchlorate is added to about parts of diethyl ether. Fluorination is carried out under the conditions set forth in example I. Infrared analysis of the isolated product produced showed it to be fluorine perchlorate.

when the foregoing example is repeated, using carbon tetrachloride rather than diethyl ether as the moderator, fluorine perchlorate is obtained in good yield.

In the preparation of the inorganic fluoro compounds of this invention, it is sometimes desirable to agitate the ingredients so as to insure more complete contact and thus improve the rate of reaction. Agitation is especially desirable in those cases where the ionic material being fluorinated is only partially soluble in the moderator.

The inorganic fluoro compounds produced according to this invention which contain energetic groups such as the nitrate group, perchloryl group, etc., are inherently useful as explosives. in addition, the novel compounds of the formula F N,O produced according to this invention find application as high energy components in rocket fuel formulations. For example, these compounds are useful as oxidizers for liquid rocket fuels such as hydrazine. Compounds such as perchloryl fluoride are well known, and are used commercially as fluorinating agents.

It will be understood that various modifications may be made in this invention without departing from the spirit thereof or the scope of the appended claims.

What is claimed is:

l. The method of preparing fluorine perchlorate which comprises reacting a perchlorate salt with fluorine in the presence of a substantially inert moderator selected from the group consisting of lower alkanols, lower alkylenc glycols and water with the weight ratio of the moderator to the salt being fluorinated in excess of 0.5, said reaction of the perchlorate salt and fluorine providing fluorine perchlorate, and recovering fluorine perchlorate as the product of the method.

2. A method in accordance with claim 1 wherein the weight ratio of moderator to the salt being fluorinated is in the range of 0.5 to 200.

3. The process for making fluorine perchlorate which comprises reacting elemental fluorine with aqueous alkali metal perchlorate to provide fluorine perchlorate, and recovering the fluorine perchlorate as the product of the process.

4. The process for making fluorine perchlorate which comprises reacting elemental fluorine with aqueous sodium perchlorate to provide fluorine perchlorate, and recovering the fluorine perchlorate as the product of the process.

5. The process for making fluorine perchlorate which comprises introducing fluorine gas into a reaction vessel containing an aqueous solution of alkali metal perchlorate to effect the reaction of the fluorine and perchlorate to produce fluorine perchlorate, and recovering the fluorine perchlorate as the product of the process. 

2. A method in accordance with claim 1 wherein the weight ratio of moderator to the salt being fluorinated is in the range of 0.5 to
 200. 3. The process for making fluorine perchlorate which comprises reacting elemental fluorine with aqueous alkali metal perchlorate to provide fluorine perchlorate, and recovering the fluorine perchlorate as the product of the process.
 4. The process for making fluorine perchlorate which comprises reacting elemental fluorine with aqueous sodium perchlorate to provide fluorine perchlorate, and recovering the fluorine perchlorate as the product of the process.
 5. The process for making fluorine perchlorate which comprises introducing fluorine gas into a reaction vessel containing an aqueous solution of alkali metal perchlorate to effect the reaction of the fluorine and perchlorate to produce fluorine perchlorate, and recovering the fluorine perchlorate as the product of the process. 